Chemical Synthesis and Materials Discovery

Functional materials impact every area of our lives ranging from electronic and computing devices to transportation and health. In this Perspective, we examine the relationship between synthetic discoveries and the scientific breakthroughs that they have enabled. By tracing the development of some important examples, we explore how and why the materials were initially synthesized and how their utility was subsequently recognised. Three common pathways to materials breakthroughs are identified. In a small number of cases, such as the aluminosilicate zeolite catalyst ZSM-5, an important advance is made by using design principles based upon earlier work. There are also rare cases of breakthroughs that are serendipitous, such as the buckyball and Teflon(R). Most commonly, however, the breakthrough repurposes a compound that is already known and was often made out of curiosity or for a different application. Typically, the synthetic discovery precedes the discovery of functionality by many decades; key examples include conducting polymers, topological insulators and electrodes for lithium-ion batteries.Comment: 15 pages, two figure

Synthesis, Crystal Structure and Properties of a Perovskite-Related Bismuth Phase, (NH4)3Bi2I9

Organic-inorganic halide perovskites, especially methylammonium lead halide, have recently led to a remarkable breakthrough in photovoltaic devices. However, due to the environmental and stability concerns of the heavy metal, lead, in these perovskite based solar cells, research in the non-lead perovskite structures have been attracting increasing attention. In this study, a layered perovskite-like architecture, (NH4)3Bi2I9, was prepared in solution and the structure was solved by single crystal X-ray diffraction. The results from DFT calculations showed the significant lone pair effect of the bismuth ion and the band gap was measured as around 2.04 eV, which is lower than the band gap of CH3NH3PbBr3. Conductivity measurement was also performed to examine the potential in the applications as an alternative to the lead containing perovskites

Open-framework zinc and cobalt phosphates synthesized by the tributylphosphate route

By employing tributylphosphate as the source of phosphorus, several open-framework zinc and cobalt phosphates have been prepared hydrothermally. Of the three new zinc phosphates [C6N2H18][Zn(HPO4)2], I, has a linear chain structure while [C4N2H14][Zn5(PO4)4(H2O)], II, [NH4][H3O][Zn4(PO4)3]2·H2O, III, have three-dimensional structures. Of the three new cobalt phosphates described, [C5N2H14][Co(HPO4)2], IV, and [C5N2H14][Co(HPO4)2], V, have linear chain structures, while [C4N2H12]3 [Co2(OH)(HPO4)3]2, VI, has a complex double chain structure. The study shows that the use of the organophosphate yields a variety of architectures of metal phosphates

Defects and disorder in metal organic frameworks.

The wide-ranging properties of metal organic frameworks (MOFs) rely in many cases on the presence of defects within their structures and the disorder that is inevitably associated with such defects. In the present work we review several aspects of defects in MOFs, ranging from simple substitutional defects at metal cation or ligand positions, to correlated defects on a larger length scale and the extreme case of disorder associated with amorphous MOFs. We consider both porous and dense MOFs, and focus particularly on the way in which defects and disorder can be used to tune physical properties such as gas adsorption, catalysis, photoluminescence, and electronic and mechanical properties.The authors would like to thank Ras Al Khaimah Center for Advanced Materials (AKC, TDB), Trinity Hall (TDB), and the ERC (ALG, Grant 279705).This is the author accepted manuscript. The final version is available from RSC via http://dx.doi.org/10.1039/C5DT04392